The present invention relates to mono- and di-(halogenmethyl)-diphenyldiiodides, -dibromides and -diamines; mono- and di-(hydroxymethyl)-diphenyldiiodides, -dibromides and -diamines and mono- and di-(aminomethyl)-diphenyldiiodides, -dibromides and -diamines; mono- and di-(hydroxymethyl)-diphenyldiphosphines and mono- and di-(aminomethyl)-diphenyldiphosphines, as well as 2-hydroxypropane-1,3-dioxyl-diphenyldiphosphines; mono- and di-(hydroxymethyl)-diphenyldiphosphines and mono- and di-(aminomethyl)-di-phenyldiphosphines, as well as 2-hydroxypropane-1,3-dioxyl-diphenyldiphosphines, the hydroxyl groups or amino groups of which are provided with functional groups via a bridging group; inorganic and organic polymeric carriers which are immobilised with said diphosphines; metal complexes of the monomeric and immobilised diphosphines; and the use of the metal complexes as homogeneous and enantioselective catalysts in the synthesis of organic compounds, for example hydrogenation.
In Pure and Appl. Chem., Vol. 68, No. 1, pp. 131-138 (1996), R. Schmid et al. describe atropisomeric 6,6xe2x80x2-dimethyl- and 6,6xe2x80x2-dimethoxy-2,2xe2x80x2-diphenyldiphosphines as chiral ligands in metal complexes, which are used for the hydrogenation of prochiral ketones and olefins, whereby high optical yields may be attained. The catalysts can only be extracted from the reaction mixtures with difficulty and incompletely, so that it is impossible to reuse them for further reactions.
In WO 98/01457, B. Pugin et al. describe the functionalisation of chiral ferrocenyl-diphosphines as ligands for metal complexes and the immobilisation on inorganic and organic carriers, which may be used as enantioselective hydrogenation catalysts. These catalysts may be easily separated from the reaction mixture and reused.
It has now been found that, in a simple manner, functionalised 2,2xe2x80x2-diphenyldiphosphines can be prepared and may be immobilised both on inorganic and on organic polymeric carriers, and can also be used as water-soluble and/or extractable and/or adsorbable ligands/catalysts. The immobilised diphosphine ligands bond with d-8 metals such as rhodium, ruthenium and iridium complexes which may be used as highly effective catalysts in enantioselective hydrogenation of carbon-carbon, carbon-nitrogen or carbon-oxygen double bonds. The selectivity, activity and total yield for immobilised systems are surprisingly high.
The catalysts may be easily separated from the reaction solution and reused. Almost no metal or ligand losses occur. In addition, immobilised diphenyldiphosphine ligands especially on inorganic carriers have surprisingly high stability, which is especially important for reusage. Therefore, using these immobilised catalysts, large-scale hydrogenation may be carried out especially economically.
The reaction to be catalysed may be carried out even heterogeneously or homogeneously through the choice of polymer, for example in the case of polymer-bound diphosphine ligands. The polymer may be prepared in such a way, or also subsequently specifically modified in such a way that the polymer-bound catalyst dissolves in the reaction medium, and can be easily separated after the reaction by filtration, ultrafiltration, extraction or adsorption on carriers, and then reused. The catalysts can be reused several times. Through the choice of polymer, the catalyst may be optimally adapted to the reaction medium during the hydrogenation step, and then completely separated, which is important in particular for hydrogenation carried out on a large scale.
The production of these immobilised or extractable and/or adsorbable diphenyldiphosphines is made possible only by providing correspondingly functionalised diphenyldiphosphines. Therefore, particular importance is placed on these intermediates and their preparation.
In all cases, recovery of the noble metals contained therein is simplified if the catalyst has to be exchanged after frequent recycling. Frequently, further purification of the hydrogenated product can be dispensed with, since the catalyst can be removed practically quantitatively.
A first object of the invention is compounds of formula 1, 
wherein
R1 is methyl chloride, methyl bromide or methyl iodide, R2 is C1-C4-alkyl or C1-C4-alkoxy or has the same significance as R1, and R3 is Br, I or xe2x80x94NH2.
R1 is preferably methyl bromide. R2 is preferably alkyl, and as alkyl preferably signifies ethyl and most preferably methyl. R2 as alkoxy preferably signifies methoxy or ethoxy. R3 is preferably Br or I.
The preparation thereof may be effected in known manner by the radical halogenation of the methyl groups of 2,2xe2x80x2-di-R3-6,6xe2x80x2-dimethyl-diphenyl with appropriate halogenation agents, for example Cl2, Br2, I2, interhalogen compounds such as ClBr, ClI, or SOCl2, SOBr2, SOI2, and organic halogen compounds such as CF3CL, CF3Br, CF3I, CCl3I, as well as N-halogenated acid amides, for example N-chloro-, -bromo- and -iodosuccinimide. Depending on the amount of halogenation agent, mono- or dihalogen-methyl-diphenyls are primarily obtained, whereby mixtures of the compounds may be separated by distillation, by chromatographic methods or by crystallisation. The oily or crystalline compounds of formula I are valuable initial products for the production of atropisomeric diphosphines.
A further object of the invention is compounds of formula II, 
wherein
R3 is Br, I or xe2x80x94NH2, R4 is hydroxymethyl, aminomethyl, hydroxy-, amino- or cyano-C2-C8-alkoxy, hydroxy-, amino- or cyano-C2-C8-alkoxymethyl, or hydroxy-, amino- or cyano-C2-C8-alkylaminomethyl, and R5 has the same significance as R4, or R5 is C1-C4-alkyl or C1-C4-alkoxy, or R4 and R5 together are HOCH(CH2xe2x80x94Oxe2x80x94)2, H2NCH(CH2xe2x80x94Oxe2x80x94)2, or hydroxy-, amino- or cyano-C2-C8-alkylOCH(CH2xe2x80x94Oxe2x80x94)2.
R3 is preferably Br or I and especially I. C2-C8-alkyl in the hydroxy-, amino- or cyanoalkyl groups is preferably C2-C6-alkyl, more preferably C2-C4-alkyl, for example C2-, C3-alkyl or C4-alkyl. R5 as C1-C4-alkyl or C1-C4-alkoxy may be for example methyl, ethyl, propyl, butyl, methoxy, ethoxy, propyloxy and butyloxy; methyl and methoxy are preferred. If R5 signifies alkyl, R4 is preferably hydroxymethyl, aminomethyl, hydroxy-, amino- or cyano-C2-C8-alkoxymethyl, or hydroxy-, amino- or cyano-C2-C8-alkylaminomethyl If R5 signifies alkoxy, R4 is preferably amino- or cyano-C2-C8-alkoxy. The hydroxy, amino or cyano groups are preferably primary groups.
The compounds of formula II may be produced by known synthesis methods. Thus, the methyl halide group in the compounds of formula I can be hydroxylated or aminated in known manner. These hydroxy or amino compounds, or the known 2-alkoxy-2xe2x80x2-hydroxy-6,6xe2x80x2-substituted diphenyl, or the known 2,2xe2x80x2-dihydroxy-6,6xe2x80x2-substituted diphenyl, or a compound of formula 
which is obtainable by reacting 2,2xe2x80x2-dihydroxy-6,6xe2x80x2-substituted diphenyl with epichlorohydrin or 1,3-dichloro-2-hydroxypropane, is reacted with cyanoalkenyl and then the cyano group is hydrogenated, or reacted with hydroxyhalogen- or aminohalogen-alkanes, or with ethylene oxide or aziridine. The HO group may be substituted by a NH2 group in known manner, for example first of all halogenated and then reacted with 1,1xe2x80x2-carbonyl-diimidazole; hydrolysis then yields the free amine.
The compounds of formula II are eminently suitable for producing corresponding diphenyldiphosphines, in which the functional groups may undergo prior or subsequent modification in conventional manner by conversion into other functional groups or by a reaction with difunctional chain extenders, for example epoxides, hydroxyalkyl cyanates, halo-alkanols, halo-alkane nitrites, halo-alkane phthalimides, dicarboxylic acids or diisocyanates. The phosphine groups are introduced in known manner [see Pure and Appl. Chem., Vol. 68, No. 1, pp. 131-138 (1996)] by reacting compounds of formula II with lithium alkyls, for example lithium butyl, and reacting these with secondary phosphine halides, for example chlorides. The functional groups may be provided with appropriate protecting groups, a large number of which are known. The introduction of the phosphine groups may also take place in stages, whereupon unsymmetrically substituted diphenyldiphosphines are obtainable. This functionalisation is described in detail in WO 98/01457.
Further objects of the invention are also the compounds of formula III, 
wherein
R6 and R7 signify identical or different secondary phosphino,
R8 is xe2x80x94CH2xe2x80x94OH, xe2x80x94CH2xe2x80x94NH2, xe2x80x94CH2xe2x80x94Oxe2x80x94Bxe2x80x94(FU)p, xe2x80x94CH2xe2x80x94NRxe2x80x2xe2x80x94Bxe2x80x94(FU)p, or xe2x80x94Oxe2x80x94Bxe2x80x94(FU)p,
R9 has the same significance as R8 or is C1-C4-alkyl or C1-C4-alkoxy, or
R8 and R9 together signify HOCH(CH2xe2x80x94Oxe2x80x94)2, H2NCH(CH2xe2x80x94Oxe2x80x94)2, (FU)pxe2x80x94Bxe2x80x94OCH(CH2xe2x80x94Oxe2x80x94)2 or (FU)pxe2x80x94Bxe2x80x94Rxe2x80x2NCH(CH2xe2x80x94Oxe2x80x94)2,
Rxe2x80x2 is H or C1-C4 alkyl;
B is a bridging group,
FU is a functional group,
p is a number from 1 to 6, and
NH2 groups are present as such or as masked isocyanate groups.
In formula III, p is preferably a number from 1 to 4, most preferably 1 to 3. Preferred compounds having more than one functional group are those of formula IIIb 
wherein R6 and R7 are defined as above, R9 is C1-C4-alkyl and preferably methyl, R101is C2-C12-, preferably C2-C6-, most preferably C2 to C4-alkylene, Xxe2x80x3 is xe2x80x94COOH and Xxe2x80x2xe2x80x3 is xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94 or xe2x80x94N(C1-C4-alkyl), as well as the amides, esters and salts thereof, especially alkali or alkaline earth metal salts.
If R8 and R9 contain a primary amino group, this may be converted by known methods into masked isocyanate groups, which similarly represent valuable functional groups.
The secondary phosphino may correspond to formula xe2x80x94PR10R11, wherein R10 and R11, independently of one another, are C1-C12-alkyl, C5-C12-cycloalkyl; phenyl, C5-C12-cycloalkyl substituted by C1-C4-alkyl or C1-C4-alkoxy; or phenyl mono- to trisubstituted by C1-C4-alkyl, C1-C4-alkoxy, xe2x80x94SiR12R13R14, halogen, xe2x80x94SO3M, xe2x80x94CO2M, xe2x80x94PO3M, xe2x80x94NR15R16, xe2x80x94[+NR15R16R17]Xxe2x88x92 or C1-C5-fluoroalkyl; R10 and R11 together are tetra- or pentamethylene either unsubstituted or mono- to trisubstituted by C1-C4-alkyl, C1-C4-alkoxy, xe2x80x94SiR12R13R14, halogen, xe2x80x94SO3M, xe2x80x94CO2M, xe2x80x94PO3M, xe2x80x94NR15R16, xe2x80x94[+NR15R16R17]Xxe2x88x92 or C1-C5-fluoroalkyl, or the group xe2x80x94PR10R11 represents a radical of formulae 
and R12, R13 and R14 independently of one another, are C1-C12-alkyl or phenyl R15 and R16, independently of one another, are H, C1-C12-alkyl or phenyl, or R15 and R16 together are tetramethylene, pentamethylene or 3-oxa-1,5-pentylene;
R17 is H or C1-C4-alkyl;
M is H or an alkali metal;
X is the anion of a monobasic acid;
halogen is fluorine, chlorine, bromine or iodine.
The alkyl and alkoxy substituents in question may be, for example, methyl, ethyl, n- and isopropyl, n-, iso- and tert.-butyl, methoxy, ethoxy, n- and isopropoxy, n-, iso- and tert.-butoxy.
R10 and R11 in the definition of alkyl may be linear or branched and they preferably contain 1 to 8, most preferably 1 to 4 carbon atoms. Examples of this alkyl are methyl, ethyl, n- and isopropyl, n-, iso- and tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. Preference is given to methyl, ethyl, n- and isopropyl, n-, iso- and tert.-butyl. If R10 and R11 are identical, then as alkyl they most preferably signify isopropyl or tert.-butyl.
R10 and R11 in the definition of cycloalkyl preferably contain 5 to 8, most preferably 5 or 6 ring carbon atoms. Examples of cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl and cyclododecyl. Preference is given to cyclopentyl and cyclohexyl, and especially cyclohexyl.
The cycloalkyl may be substituted, for example by 1 to 3 alkyl or alkoxy substituents; examples of such substituents have already been given. Preference is given to methyl and ethyl, as well as methoxy and ethoxy. Examples of substituted cycloalkyl are methyl- and methoxycyclopentyl and cyclohexyl.
R10 and R11 in the definition of substituted phenyl preferably contain 1 or 2 substituents. Where phenyl contains 2 or 3 substituents, these may be identical or different. Examples of alkyl and alkoxy substituents have already been given; preferred alkyl and alkoxy substituents for phenyl are methyl, ethyl and methoxy and ethoxy.
If the phenyl substituent is halogen, this is preferably xe2x80x94F, xe2x80x94Cl and xe2x80x94Br.
If the phenyl substituent is C1-C5-fluoroalkyl, this is partly or wholly fluorinated C1-C-alkyl. Examples thereof are the position isomers of mono- to decafluoropentyl, mono- to octafluorobutyl, mono- to hexafluoropropyl, mono- to tetrafluoroethyl and mono- and difluoromethyl. Of the partly fluorinated alkyl radicals, those of formulae xe2x80x94CF2H and xe2x80x94CF2(C1-C4-alkyl) are preferred in particular. A perfluorinated alkyl is especially preferred. Examples thereof are perfluoropentyl, perfluorobutyl, perfluoropropyl, perfluoroethyl and in particular trifluoromethyl. The fluorine-substituted alkyl groups are preferably bonded in positions 3, 4 and 5.
R12, R13 und R14 may be linear or branched alkyl, which preferably contains 1 to 8, most preferably 1 to 4 carbon atoms. Examples of alkyl have already been given. The preferred alkyl is methyl, ethyl, n-propyl, n-butyl and tert.-butyl. The substituent xe2x80x94SiR12R13R14 is most preferably trimethylsilyl.
Of the acidic phenyl substituents xe2x80x94SO3M, xe2x80x94CO2M and xe2x80x94PO3M, the group xe2x80x94SO3M and xe2x80x94CO2M is preferred. M is preferably H, Li, Na and K.
R16 and R17 as alkyl preferably contain 1 to 6, most preferably 1 to 4 carbon atoms. The alkyl is preferably linear. Preferred examples are methyl, ethyl, n-propyl and n-butyl. R18 as alkyl is preferably methyl.
Xxe2x88x92 as the anion of a monobasic acid is preferably Clxe2x88x92, Brxe2x88x92 or the anion of a carboxylic acid or sulphonic acid, for example formate, acetate, trichloroacetate or trifluoroacetate. Preferred examples of R10 and R11 as substituted phenyl are 2-methyl-, 3-methyl-, 4-methyl-, 2- or 4-ethyl-, 2- or 4-isopropyl-, 2- or 4-tert.-butyl-, 2-methoxy-, 3-methoxy-, 4-methoxy-, 2- or 4-ethoxy-, 4-trimethylsilyl-, 2- or 4-fluoro-, 2,4-difluoro-, 2- or 4-chloro-, 2,4-dichloro-, 2,4-dimethyl-, 3,5-dimethyl-, 2-methoxy-4-methyl-, 3,5-dimethyl-4-methoxy-, 3,5-dimethyl-4-(dimethylamino)-, 2- or 4-amino-, 2- or 4-methylamino-, 2- or 4-(dimethylamino)-, 2- or 4xe2x80x94SO3Hxe2x80x94, 2- or 4xe2x80x94SO3Naxe2x80x94, 2- or 4-[+NH3Clxe2x88x92]xe2x80x94, 3,4,5-trimethylphen-1-yl, 2,4,6-trimethylphen-1-yl, 4-trifluoromethyl-phenyl or 3,5-di-(trifluoromethyl)-phenyl.
Especially preferred examples of R10 and R11 are cyclohexyl, tert.-butyl, phenyl, 2- or 4-methylphen-1-yl, 2- or 4-methoxyphen-1-yl, 2- or 4-(dimethylamino)phen-1-yl, 3,5-dimethyl-4-(dimethylamino)phen-1-yl and 3,5-dimethyl-4-methoxyphen-1-yl, but most preferably cyclohexyl, phenyl, 4-methylphen-1-yl and tert.-butyl.
Another preferred group of compounds is obtained if R10 and R11 signify unsubstituted phenyl or mono- or disubstituted phenyl.
A further group of especially preferred compounds is obtained if R10 and R11 are identical and denote phenyl, cyclohexyl, 2- or 4-methylphen-1-yl, 2- or 4-methoxyphen-1-yl, 2- or 4-(dimethylamino)phen-1-yl, 3,5-dimethyl-4-(dimethylamino)phen-1-yl and 3,5-dimethyl-4-methoxyphen-1-yl; R10 and R11 are most preferably identical radicals and signify cyclohexyl or phenyl.
In the context of this invention, functional group means that this group forms a chemical bond by addition or substitution with other functional groups.
At the functional groups, chain lengthening may be undertaken for example and/or a polymerisable group may be bonded by known methods. Known methods are for example etherification, esterification, amidation, urea formation and urethane formation.
Processes for the derivatisation of functional groups are known from organic chemistry textbooks (E. Breitmaier, Gxc3xcnther Jung; Organische Chemie II (1983); Georg Thieme Verlag Stuttgart, New York pp.342, 409ff).
Examples of C-bonded functional groups are the carboxylic acid, carboxylate, carboxylic acid ester, carboxylic acid amide, carboxylic acid halide, cyano, imino, aldehyde, ketone, amine, alcohol, isocyanate, halogen or glycidyl group.
The functional group may also be a polymerisable group, and in this case is preferably a vinyl group that is unsubstituted or substituted by C1-C4-alkyl. It may be bonded, for example, by an amide or ester group to the bridging group.
The polymerisable group may be derived from ethylenically unsaturated alcohols, amines and isocyanates, for example allyl alcohol, allyl amine, allyl isocyanate, croton alcohol; monoesters or monoamides of dicarboxylic acids and unsaturated alcohols and amines; functional styrenes, for example chloromethylstyrene, hydroxystyrene, hydroxyethoxystyrene, styreneamine, styrene-hydroxyethylamine, styrenecarboxylic acid, styrenesulphonic acid, vinyl hydroxyethylether, acrylic acid, methacrylic acid, acrylic and methacrylic acid amide, acrylic- and methacrylic acid-C2-C6-hydroxyalkyl-amide, acrylic- and methacrylic acid-C2-C6-hydroxyalkyl-ester.
The functional group which is bonded by a bridging group B to one of its carbon atoms preferably signifies an amine, alcohol, isocyanate, carboxylic acid, carboxylic acid ester, carboxylic acid amide, carboxylic acid halide group or a polymerisable group.
Linkage by means of these functional groups may be carried out by generally known processes. It is fundamentally also possible to transform existing functional groups into other functional groups, for example xe2x80x94CH2OH groups by oxidation into carboxylic acids, carboxylic acids into amides or halides, amine groups into isocyanate groups, alcohols or amines into carbonates or urethanes. Furthermore, it is possible to react alcohols or amines first of all with halocarboxylic acids (for example chloroacetic acid). Chain extenders, for example epoxides, aziridines, diols, diamines, dicarboxylic acids or dicarboxylic acid esters and diisocyanates, may also be used once or repeatedly in series, thus specifically determining the length of the extending group. These linking methods and processes are known and are described in specialist literature.
If the functional group FU signifies (O)Cxe2x80x94H, (O)Cxe2x80x94(C1-C12)-alkyl, COOH, COCl or COO(C1-C6)-alkyl, these groups can also be converted into other functional groups by reduction, transesterification or other known standard reactions from organic chemistry. For example, the aldehyde group is easily converted into an amine group by means of a reaction with an amine and subsequent hydrogenation. Reduction to the alcohol with, for example, LiAlH4 is likewise possible.
If the functional group signifies OH, NH2 or NH(C1-C12-alkyl), it can be functionalised to an oxyalkylsilyl group by means of a reaction with a compound of formula (R18)n(R19O)3-nxe2x80x94Sixe2x80x94R20xe2x80x94NCO, whereby R20 is C1-C12-alkylene, R19 is C1-C12 alkyl, R18 is C1-C12alkyl or OR19 and n is 0, 1 or 2.
The bridging group B may contain 1 to 30 atoms, preferably 1 to 20 atoms, and most preferably 1 to 12 atoms in the chain, selected from the group C, O, S and N. The bridging group in question is preferably hydrocarbon radicals, that may be interrupted by one or more hetero atoms from the group O, S and N and/or the group C(O).
The bridging group B may correspond to formula (IV)
xe2x80x94(R100)xe2x80x94X1xe2x80x94xe2x80x83xe2x80x83(IV), 
wherein X1 is a direct bond, or X1 is selected from the group xe2x80x94C(O)xe2x80x94, xe2x80x94Oxe2x80x94C(O)xe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94Oxe2x80x94SO2xe2x80x94, xe2x80x94NR101xe2x80x94C(O)xe2x80x94, xe2x80x94NR101xe2x80x94C(O)xe2x80x94, xe2x80x94NR101SO2xe2x80x94 or xe2x80x94NR101xe2x80x94SO2xe2x80x94, wherein
R101 is H or C1-C30-alkyl, C5- or C6-cycloalkyl, C5- or C6-cycloalkylmethyl or -ethyl, phenyl, benzyl or 1-phenyleth-2-yl
and R100 is a bivalent bridging group.
R101 defined as alkyl preferably contains 1 to 6, most preferably 1 to 4 carbon atoms. Some examples are methyl, ethyl, n- or isopropyl, butyl, hexyl and octyl. R101 defined as cycloalkyl is preferably cyclohexyl, and defined as cycloalkylmethyl is cyclohexylmethyl. In a preferred embodiment, R101 is H or C1-C4-alkyl.
The bivalent bridging group R100 is preferably a hydrocarbon radical, which preferably contains 1 to 30, more preferably 1 to 18, most preferably 1 to 12, particularly preferably 1 to 8 carbon atoms, and is unsubstituted or mono- or polysubstituted by C1-C4-alkyl, C1-C4-alkoxy or xe2x95x90O. The hydrocarbon radical may also be interrupted once or many times by hetero atoms selected from the group xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94 and xe2x80x94NR101xe2x80x94, whereby R101 is preferably H or C1-C4-alkyl.
The bivalent bridging groups R100 may be for example C1-C20-, preferably C2-C12-alkyls, which can be linear or branched. Some examples are methylene, ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, pentylene, hexylene, octylene, dodecylene, tetradecylene, hexadecylene and octadecylene.
The bivalent bridging group R100 may be for example polyoxaalkylene with 2 to 12, preferably 2 to 6, most preferably 2 to 4 oxyalkylene units and 2 to 4, preferably 2 or 3 carbon atoms in the alkylene. It is most preferably polyoxyethylene and polyoxypropylene with 2 to 6 oxyalkylene units.
The bivalent bridging group R100 may be for example C5-C12-, preferably C5-C8-, most preferably C5- or C6-cycloalkyl, for example cyclopentylene, cyclohexylene, cyclooctylene or cyclododecylene.
The bivalent bridging group R100 may be for example C5-C12-, preferably C5-C8-, most preferably C5- or C6-cycloalkyl-C1-C12- and preferably xe2x80x94C1-C4-alkyl. Some examples are cyclopentyl-CnH2nxe2x80x94 and cyclohexyl-CnH2nxe2x80x94, wherein n is a number from 1 to 4. -Cyclohexyl-CH2xe2x80x94 is preferred in particular.
The bivalent bridging group R100 may be for example C5-C12xe2x80x94, preferably C5-C8xe2x80x94, most preferably C5- or C6-cycloalkyl-(C1-C12-alkyl)2xe2x80x94 and preferably (xe2x80x94C1-C4-alkyl)2. Some examples are cyclopentyl-(CnH2nxe2x80x94)2 and cyclohexyl-(CnH2nxe2x80x94)2, wherein n is a number from 1 to 4. xe2x80x94CH2-cyclohexyl-CH2xe2x80x94 is preferred in particular.
The bivalent bridging group R100 may be for example C6-C14-arylene and preferably C6-C10-arylene, for example naphthylene or more preferably phenylene.
The bivalent bridging group R100 may be for example C7-C20-aralkylene and preferably C7-C12-aralkylene More preferred is arylene-CnH2nxe2x80x94, wherein arylene is naphthylene and especially phenylene and n is a number from 1 to 4. Examples are benzylene and phenylethylene.
The bivalent bridging group R100 may be for example arylene-(CnH2nxe2x80x94)2xe2x80x94, wherein arylene is preferably naphthylene and especially phenylene, and n is a number from 1 to 4. Examples are xylylene and phenylene(CH2CH2)2xe2x80x94.
A preferred group of compounds is formed if B signifies unsubstituted linear or branched C1-C12-alkylene, C2-C12-alkenylene, C2-C12-alkynylene, C5-C12-cycloalkylene, C5-C12-cycloalkenylene, phenylene, phenylene-(C1-C12)-alkylene, or B signifies linear or branched C1-C12-alkylene, C2-C12-alkenylene, C2-C12-alkynylene, C5-C12-cycloalkylene, C5-C12-cycloalkenylene, phenylene or phenylene-(C1-C12)-alkylene substituted by C1-C4-alkyl, C1-C4-alkoxy, halogen or hydroxy, and
FU is halogen, OH, NH2, NH(C1-C12)-alkyl, (O)Cxe2x80x94H, (O)Cxe2x80x94(C1-C12)-alkyl, COOH, COCl, COO(C1-C6)-alkyl, xe2x80x94NCO or a group OC(O)xe2x80x94CRcxe2x95x90CRdRe or OC(NRf)xe2x80x94CRcxe2x95x90CRdRe, wherein Rc, Rd, Re und Rf independently of one another, signify hydrogen, C1-C6-alkyl or phenyl.
If group B signifies linear or branched C1-C12-alkylene, C2-C12-alkenylene, C2-C12-alkynylene, C5-C12-cycloalkylene, C5-C12-cycloalkenylene, phenylene or phenylene-(C1-C12)-alkylene substituted by halogen or hydroxy, then at least two functional centres may be present together with the functional group FU, and these can be used for further reactions or for chain extending.
B is most preferably unsubstituted or halogen- or OH-substituted linear or branched C1-C12-alkylene.
Examples of alkylene are methylene, ethylene, the various position isomers of propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene. Examples of substituted alkylenes are 1- or 2-hydroxypropylene, 1-, 2- or 3-hydroxybutylene, the various position isomers of chloropropylene and chlorobutylene. Examples of alkenylene are propenylene, butenylene, pentenylene or hexenylene.
B as cycloalkylene preferably contains 5 to 8, most preferably 5 or 6 ring carbon atoms.
Examples of cycloalkylene are cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclodecylene, cycloundecylene and cyclododecylene. Preference is given to cyclopentylene and cyclohexylene, and especially cyclohexylene. Cycloalkylene may be substituted by C1-C4-alkyl, C1-C4-alkoxy, halogen or hydroxy. Examples of such substituents have already been given. Preferred substituents are halogen, OH, methyl and ethyl, as well as methoxy and ethoxy. Examples of substituted cycloalkylene are hydroxycyclohexylene, methyl- and methoxycyclopentylene and -cyclohexylene.
Examples of cycloalkenylene are cyclopentenylene, cyclohexenylene, cycloheptenylene, cyclooctenylene, cyclodecenylene, cycloundecenylene and cyclododecenylene. Preference is given to cyclopentenylene and cyclohexenylene, and especially cyclohexenylene.
B when defined as phenylene or phenylene-(C1-C12)-alkylene, substituted by C1-C4-alkyl, C1-C4-alkoxy, halogen or hydroxy, preferably contains 1 or 2 substituents. Where phenylene contains 2 or 3 substituents, these may be identical or different. Examples of alkyl and alkoxy substituents have already been given; preferred alkyl and alkoxy substituents for phenylene are methyl, ethyl and methoxy and ethoxy. If the phenylene substituent is halogen, this is preferably xe2x80x94F, xe2x80x94Cl and xe2x80x94Br. Preferred phenylene-C1-C12)-alkylene are phenylenepropylene, phenyleneethylene or the benzylene group.
Some preferred examples of compounds of formula III are those of formula 
wherein R6 and R7 denote identical or different secondary phosphine groups,
R21 is H, NH2(CH2)3xe2x80x94, (C1- or C2-alkoxy)3Si(CH2)3NHC(O)xe2x80x94,
R22 signifies HOCH2xe2x80x94, H2NCH2xe2x80x94, NCxe2x80x94(CH2)2xe2x80x94OCH2xe2x80x94H2Nxe2x80x94(CH2)3xe2x80x94OCH2xe2x80x94 or H2Nxe2x80x94(CH2)3xe2x80x94HNCH2xe2x80x94,
R23 is HOxe2x80x94(CH2)2xe2x80x94Oxe2x80x94 or HOxe2x80x94(CH2)3xe2x80x94Oxe2x80x94, H2Nxe2x80x94(CH2)2xe2x80x94Oxe2x80x94 or H2Nxe2x80x94(CH2)3xe2x80x94Oxe2x80x94, and R24 has the same significance as R23 or is methoxy.
A further aspect of the invention is metal complexes of formulae V, Va and Vb of d-8 metals with the compounds of formula III, 
whereby R6, R7, R8 and R9 have the above-mentioned significances and preferences;
Y denotes two monoolefin ligands or one diene ligand;
Me signifies a d-8 metal selected from the group Ir and Rh;
D is xe2x80x94Cl, xe2x80x94Br or xe2x80x94I; and
E is the anion of an oxyacid or complex acid;
X2 and X2xe2x80x2 are identical or different and have the significance of D and E, or X2 and X2xe2x80x2 are allyl or 2-methylallyl, or X2 has the significance of D and E and X2xe2x80x2 is hydride.
Metal complexes in which Y is 1,5-hexadiene, 1,5-cyclooctadiene or norbornadiene are preferred. In the metal complexes according to the invention, D is preferably xe2x80x94Cl, xe2x80x94Br or xe2x80x94I. In the preferred metal complexes, E is ClO4xe2x88x92, CF3SO3xe2x88x92, CH3SO3xe2x88x92, HSO4xe2x88x92, BF4xe2x88x92, B(Phenyl)4xe2x88x92, PF6xe2x88x92, SbCl6xe2x88x92, AsF6xe2x88x92 or SbF6xe2x88x92.
Further ruthenium complexes that may be considered are known in literature and are described for example in U.S. Pat. No. 4,691,037, U.S. Pat No. 4,739,085, U.S. Pat. No. 4,739,084, EP 269395, EP 271310, EP 271311, EP 307168, EP 366390, EP 470756, JP 08081484, JP 08081485, JP 09294932, EP 831099, EP 826694, EP 841343, J. P. Genxc3xaat, Arcos Organics Acta, 1 (1995) 4, N. C. Zanetti et al., Organometallics 15 (1996) 860.
The metal complexes of formulae V, Va or Vb are produced by methods known in literature.
The compounds of formulae V, Va and Vb represent catalysts that are already homogeneous and can be used, for example, for hydrogenation of unsaturated organic compounds.
The metal complexes are preferably used for the asymmetric hydrogenation of prochiral compounds with carbon/carbon or carbon/hetero atom multiple bonds, in particular double bonds. Hydrogenations of this type with soluble homogeneous metal complexes are described, for example, in Pure and Appl. Chem., Vol. 68, No. 1, pp. 131-138 (1996).
The compounds of formula III may be covalently bonded to inorganic or organic carriers in a simple manner. A further aspect of the invention is inorganic or organic polymeric carriers, to which diphosphines of formula III 
are bonded. These are characterised in that they are bonded by the functional group FU of radicals R8, R9 or R8 and R9 to the inorganic or polymeric organic carrier, whereby the radicals R6, R7, R8 and R9 have the above-mentioned significances and preferences.
The diphosphines of formula III are preferably bonded to the surface of these carriers. This has the advantage that catalytically active groups of corresponding d-8 metal complexes are also accessible and no inclusion occurs. In this way, during hydrogenation, less catalyst-containing carrier can also be used.
If the compounds of formula III are bonded to inorganic carriers, the functional group FU thereof is advantageously first of all reacted with an alkoxysilylalkyl isocyanate, for example a compound of formula (VI)
(R25)n(R26O)3-nSixe2x80x94R27xe2x80x94NCOxe2x80x83xe2x80x83(VI), 
wherein R27 is C1-C12-alkylene, R26 is C1-C12 alkyl, R25 is C1-C4-alkyl or OR26 and n is 0, 1 or 2; FU in formula III in this case is defined as OH, NH2 or NHxe2x80x94(C1-C12)-alkyl. Compounds of formulal (IIIa) are obtained, 
wherein the group B-FU in radicals R8 and R9 is a radical of formula
xe2x80x94X3xe2x80x94C(O)xe2x80x94NHxe2x80x94R27xe2x80x94Si(R25)n(R26O)3-n 
wherein X3 signifies xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94 or xe2x80x94N(C1-C4-alkyl), and n, R25, R26 and R27 have the abovementioned significances. These compounds are intermediates in the preparation of diphenyldiphosphines bonded to inorganic carriers.
A further aspect of the invention is a solid inorganic carrier, which is characterised in that it has diphosphine ligands of formula IIIa bonded at the surface by one or two silyl groups of the radical of formula
xe2x80x94X3xe2x80x94C(O)xe2x80x94NHxe2x80x94R27xe2x80x94Si(R25)n(R26O)3-n 
During this bonding, 1, 2 or 3 alkoxy groups in the silyl radical can be replaced by bonds.
The solid carrier in question may be silicates and semi-metal or metal oxides, as well as glass, which preferably exists as powders with average particle sizes of 10 nm to 2000 xcexcm, preferably 10 nm to 1000 xcexcm, most preferably 10 nm to 500 xcexcm. The particles may be both compact and porous. Porous particles preferably have high internal areas, for example 1 to 1200 m2, preferably 30 to 600 m2. Examples of oxides and silicates are SiO2, TiO2, ZrO2, MgO, NiO, WO3, Al2O3, La2O3, silica gels, clays and zeolites. Preferred carriers are silica gels, aluminium oxide, titanium oxide or glass and mixtures thereof. One example of glass as a carrier is xe2x80x9cControlled Pore Glassxe2x80x9d, which is available commercially.
Preparation of the diphosphine ligands of formula IIIa, which are bonded to inorganic carriers, is described in WO 98/01457.
Owing to the presence of alkoxysilane groups, the compounds of formula IIIa may also be reacted directly to polysiloxanes in a sol-gel process. Reactions of this type have been described for example by U. Deschler et al. in Angew. Chem. 98, (1986), 237-253.
A further aspect of the invention is organic polymeric carriers, to which diphenylphosphines of formula III 
are bonded by at least one xe2x80x94OH, NH2 group or functional group FU, whereby the radicals R6, R7, R8 und R9 have the above-mentioned significances and preferences. These carriers include both polymers which contain as structural elements the diphenyldiphosphines of formula III, which are bonded by at least one xe2x80x94OH, NH2 group or functional group FU, and polymer particles in which the diphenyldiphosphines of formula III, which are bonded by at least one xe2x80x94OH, NH2 group or functional group FU, are bonded to functional groups at the surface of the particles.
The organic polymeric carriers may be uncrosslinked thermoplastic, crosslinked or structurally crosslinked polymers, which contain functional groups.
The polymers containing functional groups may be either polymers of olefinically unsaturated monomers, for example polyolefins, polyacrylates, polyisoprene, polybutadiene, polystyrene, polyphenylene, polyvinychloride, polyvinylidene chloride or polyallyl compounds, polyaddition compounds, for example polyurethanes or polyethers, or polycondensated products, for example polyesters or polyamides.
The monomers which form the polymer are preferably selected from the group styrene, p-methylstyrene or xcex1-methylstyrene, which contain functional groups. Another preferred group of polymers is formed by monomers that are derived from xcex1,xcex2-unsaturated acids, their esters or amides. Particularly preferred are monomers from the group of acrylates and their C1-C4-alkylesters, methacrylates and their C1-C4-alkylesters, acrylamide and acrylonitrile. An equally preferred group is derived from monomers from the group of acrylates and their C1-C4-alkylesters, methacrylates and their C1-C4-alkylesters, which contain as structural elements, in bonded form, a hydroxyl group or a primary or secondary amine group as functional groups in the ester group.
Bonding of the diphenyldiphosphines of formula III to the polymeric carriers may take place in various ways.
One preferred group of polymerically bonded compounds of formula III is formed in such a way that FU illustrates an olefinically unsaturated radical which is bonded by an ester group OC(O)xe2x80x94CRcxe2x95x90CRdRe or an amide group OC(NRf)xe2x80x94CRcxe2x95x90CRdRe to the bridging group B, wherein Rc, Rd, Re und Rf independently of one another, are hydrogen or C1-C6-alkyl, and these are used as comonomers in the radical polymerisation of olefinically unsaturated further monomers. Examples and preferences of further monomers are mentioned above. For the remaining radicals of the compounds of formula III, the above-mentioned significances and preferences apply.
Radical polymerisation is effected in known manner, and a copolymer is obtained which contains diphenyldiphosphine ligands in bonded form.
Another possibility is a polymer-analogous reaction, such as that described by R. Cullen et. al. in J. of Organometallic Chemistry, 333 (1987), 269-280.
Polymer-analogous reactions are possible with polycondensates, such as polyesters, polyamines, which contain directly in a side chain or in the polymer chain a further functional group that is capable of condensation. Examples are hydroxyl-group-containing polyesters or polyethers, which can be reacted with compounds of formula III, whereby in this case the functional group FU preferably signifies xe2x80x94COO(C1-C12)-alkyl or xe2x80x94COCl.
A further group of preferred polymers that are suitable for polymer-analogous reactions is formed by monomers which contain vinyl alcohol as a homopolymer or vinyl alcohol as a copolymer with vinyl acetate, stearate, benzoate, maleate, vinyl butyral, allyl phthalate, allyl melamine.
Suitable polymers which are equally preferred for polymer-analogous reactions are formed from phenol and a C1-C4-aldehyde, most preferably from phenol and formaldehyde. The polymers are known as phenol-formaldehyde resins, especially as novolaks, and are available commercially.
Another preferred group of polymers which are suitable for polymer-analogous reactions is derived from bisglycidyl ethers and diols. These are hydroxyl-functional polyethers, which are produced for example from bisglycidyl ethers and bisphenol A. These polyepoxides may be built up from diepoxide comonomers with preferably 6 to 40, most preferably 8 to 30 carbon atoms, and diols as comonomers with preferably 2 to 200, most preferably 2 to 50 carbon atoms. One preferred group derived therefrom is formed from monomers, which build up a polymer from cyclic C3-C6-ethers or C2-C6-alkylene glycols with bisglycidyl ethers. The bisglycidyl ethers may be aromatic, aliphatic or cycloaliphatic.
Further preferred polymers with hydroxyl groups as functional groups are polysaccharides. Especially preferred are partial cellulose acetates, propionates or butyrates, partial cellulose ethers, starch, chitin and chitosan.
Further polymers are derived from polymers having reducible groups, for example nitrile groups, ketone groups, carboxylic acid esters and carboxylic acid amides.
Insoluble polymers may also be used in the reaction medium, and these are functionalised at the surface with hydroxyl or amine groups by means of a chemical or physical process. For example, partially unsaturated polymers are provided at their surface with hydroxyl groups by means of oxidation, e.g. with hydrogen peroxide. Another possibility is plasma treatment in, for example, an oxygen atmosphere, nitrogen atmosphere or ammonia atmosphere. The polymers are preferably present as powders. Of these carriers, polystyrene is preferred in particular, and this is subsequently functionalised by known methods with hydroxyl, amino or hydroxymethyl groups.
An especially preferred group is formed by a polymeric organic material with structural elements, in which at least one isocyanate group FU in compounds of formula III is bonded to hydroxyl or amine groups, forming a urethane or urea bond, whereby the hydroxyl or amine groups are bonded directly or in a side chain of the polymer chain. Monomers of formula III with isocyanate groups are obtainable in a simple manner by reacting diisocyanates with amine- or hydroxyl-functional compounds of formula III.
The diphenyldiphosphine radicals of formula III may be present as enantiomer mixtures. The radicals are preferably present in the form of the optically active isomers.
One preferred group of immobilised polymers according to the invention is that in which hydroxy- or amino-functional polymers are first of all reacted with one isocyanate group of diisocyanates and then the second isocyanate group is reacted with a hydroxy- or amino-functional diphosphine of formula III.
The choice of diisocyanate is in itself not critical. Suitable diisocyantes that are available on a large scale are described for example in Houben Weyl, Makromolekulare Stoffe, volume E 20, pages 1587 to 1583, 1987 edition.
Preference is given to diisocyanates with a bridging group Q, which is selected from the group linear or branched, aliphatic C2-C20-alkyl which is unsubstituted or mono- to poly-substituted by C1-C6-alkyl, C1-C6-alkoxy; C3-C8-cycloalkyl or heterocycloalkyl which is unsubstituted or mono- to polysubstituted by C1-C6-alkyl, C1-C6-alkoxy; linear or branched aliphatic C2-C20-alkyl unsubstituted or substituted by C1-C6-alkyl, C1-C6-alkoxy and interrupted by C3-C8-cycloalkyl or heterocycloalkyl which is unsubstituted or substituted by C1-C6-alkyl, C1-C6-alkoxy; phenyl, naphthyl, biphenyl or C3-C10-heteroaryl either unsubstituted or mono- to polysubstituted by C1-C6-alkyl, C1-C6-alkoxy; linear or branched aliphatic C2-C20-alkyl which is unsubstituted or substituted by C1-C6-alkyl, C1-C6-alkoxy and is interrupted by phenyl, naphthyl or C3-C10-heteroaryl.
Heterocycloalkyl is e.g. pyrrolidine, piperidine, morpholine, oxazolidine, dioxolan or an isocyanuric acid triester group.
Heteroaryl is for example pyridine, pyrimidine, pyrrole, furan, imidazole, pyrazole or triazine.
Especially preferred diisocyanates are 1,6-bis-[isocyanate]-hexane, 5-isocyanate-3-(isocyanatemethyl) -1,1,3-trimethylcyclohexane, 1,3-bis-[5-isocyanate-1,3,3-trimethyl-phenyl]-2,4-di-oxo -1,3-diazetidine, 3,6-bis-[9-isocyanate-nonyl]-4,5-di-(1-heptenyl)-cyclohexene, bis-[4-isocyanate-cyclohexyl]-methane, trans-1,4-bis-[isocyanate]-cyclohexane, 1,3-bis-[isocyanatemethyl]-benzene, 1,3-bis-[1-isocyanate-1-methyl-ethyl]-benzene, 1,4-bis-[2-cyanate-ethyl]-cyclohexane, 1,3-bis-[isocyanate-methyl]-cyclohexane, 1,4-bis-[1-isocyanate-1-methylethyl]-benzene, bis-[isocyanate]-isododecylbenzene, 1,4-bis-[isocyanate]-benzene, 2,4-bis-[isocyanate]-toluene, 2,6-bis-[isocyanate]-toluene, 2,4-/2,6-bis-[isocyanate]-toluene, 2-ethyl-1,2,3-tris-[3-isocyanate-4-methyl-anilinocarbonyloxy]-propane, N,Nxe2x80x2-bis-[3-isocyanate-4-methylphenyl]-urea, 1,4-bis-[3-isocyanate-4-methylphenyl]-2,4-dioxo-1,3-diazetidine, 1,3,5-tris-[3-isocyanate-4-methylphenyl]-2,4,6-trioxohexahydro-1,3,5-triazine, 1,3-bis-[3-isocyanate-4-methylphenyl]-2,4,5-trioxoimidazolidine, bis-[2-isocyanate-phenyl]-methane, (2-isocyanate-phenyl)-(4-isocyanate-phenyl)-methane, bis-[4-isocyanate-phenyl]-methane, 2,4-bis-[4-isocyanate-benzyl]-1-isocyanatbenzene, [4-isocyanate-3-(4-isocyanate-benzyl)-phenyl]-[2-isocyanate-5-(4-isocyanate-benzyl)-phenyl]methane, tris-[4-isocyanate-phenyl]-methane, 1,5-bis-[isocyanate]-naphthaline, or 4,4xe2x80x2-bis[isocyanate]-3,3xe2x80x2-dimethyl-biphenyl.
Particularly preferred diisocyanates are 1,6-bis-[isocyanate]-hexan, 5-isocyanate-3-(isocyanate-methyl)-1,1,3-trimethylcyclohexane, 2,4-bis-[isocyanate]-toluene, 2,6-bis-[isocyanate]-toluene, 2,4-/2,6-bis-[isocyanate]-toluene or bis-[4-isocyanate-phenyl]-methane.
The polymers to be used according to the invention, which contain hydroxyl groups and amine groups, may be uncrosslinked thermoplastic, crosslinked or structurally crosslinked polymers. Examples of hydroxyl-group-containing polymers are those mentioned ahove.
The polymers to be used according to the invention are known per se, partly commercial or may be produced by known polymerisation processes or by subsequent modification of polymers.
The polymeric organic materials preferably have a molecular weight of 5000 to 5,000,000 daltons, most preferably 50,000 to 1,000,000 daltons.
A preferred sub-group of polymeric organic materials is highly crosslinked macroporous polystyrene or polyacrylate.
Another preferred group of polymers is formed by weakly crosslinked polystyrene. An example thereof is polystyrene crosslinked with 1-5% divinylbenzene.
The particle size of the polymeric organic materials is preferably 10 xcexcm to 2000 xcexcm.
The highly crosslinked polymeric organic materials preferably have a specific area of 20 m2/g to 1000 m2/g, most preferably 50 m2/g to 500 m2g, determined by the BET method.
Production of the diphenyldiphosphines that are bonded to inorganic or organic carriers may be effected analogously to the processes described in WO 98/01457.
A further aspect of the invention is the d-8 metal complexes of inorganic or organic polymeric carriers, to which diphenyldiphosphines of formula VII, VIIa or VIIb 
are bonded by at least one HOxe2x80x94, H2Nxe2x80x94 group of functional group FU, whereby the radicals R6, R7, R8, R9, Me, E, Y, X2 and X2xe2x80x2 and the carrier have the above-mentioned significances and preferences.
Production of metal complexes with the polymeric carrier may take place by methods known in literature for the production of analogous homogeneous catalysts.
A further aspect of the invention is diphenyldiphosphine ligands of formula III and their d-8 metal complexes of formulae VII, VIIa and VIIb with a molecular weight of preferably less than 5000 daltons, which contain solubility-enhancing or adsorption-facilitating groups bonded to at least one HOxe2x80x94, H2Nxe2x80x94 or functional group FU, which groups can be separated by extraction with immiscible liquids or by adsorption on a carrier. During extraction, it is preferable to use two immiscible liquids. When using such diphenyldiphosphines and the d-8 metal complexes thereof, there is almost no loss of metal or ligand. Therefore, using these extractable or adsorbable catalysts, large-scale hydrogenation may be carried out especially economically. A preferred group of soluble compounds is those that are soluble in aqueous media.
Suitable immiscible liquids that may be mentioned are, for example, water and organic solvents that are immiscible with water, such as alkanes (for example hexane), chlorinated alkanes (for example methylene chloride, chloroform), aryls (for example toluene, benzene, xylene) or esters (for example ethyl acetate) or organic solvent systems such as fluorinated hydrocarbons and hydrocarbons.
Carriers that are suitable for adsorption are metal oxides, for example silica gel, aluminium oxide, or reversed phase silica gel, polar and apolar polymers and ion exchangers (preferably for ligands with charged radicals).
Suitable solubility-enhancing or adsorption-facilitating radicals may be taken from the publication I. T. Horvxc3xa1th et al. in Science, Vol. 266, pages 72-75 (1994).
Preferred solubility-enhancing radicals for extractable diphenyldiphosphines are, for example, lipophilic radicals which are derived from alkanes having a molecular weight of between 100 and 2000 daltons, or also hydrophilic, optionally charged radicals, which are derived from sugars, or from polymers, for example polyvinyl alcohols, polyacrylic acids, polyethylene glycols, polyvinyl toluene or dendrimers.
Preferred adsorption-facilitating radicals are, for example, lipophilic radicals which are derived from alkanes having a molecular weight of between 100 and 2000 daltons, and also fluoroalkanes.
Further examples of extractable or adsorbable radicals are those that are derived from polyethylene glycols, polyhydroxy hydrocarbons, polyamino hydrocarbons and the ammonium salts thereof, polycarboxyl hydrocarbons and the alkali metal salts thereof, polyhydroxy hydrocarbons or polyamino hydrocarbons, which are reacted with halo-carboxylic acids, polyvinyl alcohols, polyaryl acids and the alkali metal salts thereof, higher alkanes and perfluoroalkanes.
The metal complexes according to the invention are eminently suitable as catalysts for the hydrogenation of organic double and triple bonds. Examples are compounds which contain the groups Cxe2x95x90C, Cxe2x95x90N, Cxe2x95x90O, Cxe2x95x90Cxe2x80x94N or Cxe2x95x90Cxe2x80x94O (see for example K. E. Kxc3x6nig, The Applicability of Asymmetric Homogeneous Catalysis, in James D. Morrison (ed.), Asymmetric Synthesis, Vol. 5, Academic Press, 1985). The metal complexes according to the invention are especially suitable for the enantioselective hydrogenation of compounds having prochiral carbon double bonds and carbon/hetero atom double bonds. Examples of such compounds are prochiral alkenes, imines and ketones.
After the reaction, the catalysts according to the invention may be practically completely separated from the reaction mixture in a simple manner, for example by decanting, centrifuging, filtration, ultrafiltration, extraction or adsorption, and reused. One particular advantage of this is that they can be reused several times without any notable losses of activity or selectivity . The catalysts which are functionalised and immobilised according to the invention often have improved optical yields when compared with the previously known diphenylphosphine catalysts.
A further aspect of the invention is therefore the use of the metal complexes of d-8 metals according to the invention as heterogeneous or homogeneous catalysts for the asymmetric hydrogenation of prochiral compounds with carbon double bonds or carbon/hetero atom double bonds. The metal complexes are preferably used for the asymmetric hydrogenation of prochiral compounds with carbon double bonds or carbon/hetero atom double bonds, especially the Ir complexes for the hydrogenation of prochiral ketimines.
A further aspect of the invention is a process for the asymmetric hydrogenation of compounds with carbon double bonds or carbon/hetero atom double bonds, which is characterised in that the compounds are reacted at a temperature of xe2x88x9220 to 80xc2x0 C. and at a hydrogen pressure of 105 to 2xc3x97107 Pa in the presence of catalytic amounts of one or more metal complexes according to the invention.
Catalysts are preferably employed in amounts of 0.0001 to 10 mol %, more preferably 0.001 to 10 mol %, most preferably 0.01 to 5 mol %, based on the compound to be hydrogenated.
Hydrogenation may be carried out continuously or intermittently in various types of reactor. Preference is given to the reactors which allow comparatively favourable blending and good heat removal, e.g. loop reactors. This type of reactor has proved to be particularly effective when using small amounts of catalyst.
The hydrogenated organic compounds that may be produced according to the invention are active substances or intermediates for producing such substances, especially in the field of pharmaceutical and agrochemical production. For example, o,o-dialkylarylketamine derivatives, especially those with alkyl and/or alkoxyalkyl groups, have fungicidal activity, especially herbicidal activity. The derivatives in question may be amine salts, acid amides, e.g. of chloroacetic acid, tertiary amines and ammonium salts (see e.g. EP-A-0 077 755 and EP-A-0 115 470).
The following examples illustrate the invention.
A) Preparation of halomethyidiphenyl diiodides